CN103011680B - Sulfate-resistant organosilicone modified polycarboxylic superplasticizer and preparation method thereof - Google Patents
Sulfate-resistant organosilicone modified polycarboxylic superplasticizer and preparation method thereof Download PDFInfo
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- CN103011680B CN103011680B CN201210539481.4A CN201210539481A CN103011680B CN 103011680 B CN103011680 B CN 103011680B CN 201210539481 A CN201210539481 A CN 201210539481A CN 103011680 B CN103011680 B CN 103011680B
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Abstract
The invention relates to a sulfate-resistant organosilicone modified polycarboxylic superplasticizer and a preparation method thereof. A novel polycarboxylic superplasticizer is prepared from methoxy-polyoxyethylene (methyl) acrylic esters, organosilicone monomers, carboxylic acid monomers, carboxylic ester monomers and sulfonic acid monomers and the like through free radical polymerization. According to the invention, organosilicone monomers and sulfonic acid monomers are adopted for copolymerization; and by introduced silane bonds and silicate, strong chemical bonds are formed so as to resist the competitive adsorption action of sulfate-resistant ions, thereby reaching the purpose of improving a situation that the polycarboxylic superplasticizer is incompatible with a concrete material with high sulphate content.
Description
Technical field
The present invention relates to a kind of concrete admixture--poly carboxylic acid series super plasticizer and preparation method thereof, especially relate to a kind of organic-silicon-modified poly carboxylic acid series super plasticizer of novel sulfate resistance type of preparing taking methoxy polyoxyethylene (methyl) acrylate, silicone based monomer, carboxylic-acid monomer, carboxylic acid esters monomer, sulphonic acids monomer etc. as raw material and preparation method thereof.
Background technology
Concrete is consumption maximum, most widely used material of construction in the world, and recent decades, concrete technology has entered new developmental stage, and its range of application is also in further expansion.The demand for development concrete of the new technologies such as pump concrete, self-leveling concrete, non-dispersible underwater concrete, sprayed concrete, polymer concrete, high-strength high-performance concrete have adjust solidifying, reduce the performances such as hydration heat, degree of mobilization, high-strength, lightweight and high-durability.Also require that preparation energy consumption is low, cost is low, be suitable for the concrete of rapid construction simultaneously.The features such as application admixture is the main path of concrete technology progress, and it can make concrete meet various construction requirement, has less investment, and instant effect is applied easily, and technical economic benefit is remarkable.And cement water reducing agent is the widest, the maximum one of consumption of application surface in concrete admixture.In the water reducer development course of nearly 70 years, three developmental stage from ordinary water-reducing agent to high efficiency water reducing agent are experienced: the first-generation water reducer such as the sulfonated lignin just brought into use from the thirties in 20th century, sodium abietate, stearate soap; The s-generation high efficiency water reducing agents such as the naphthalene system bringing into use from the sixties in 20th century, fatty family, melamine series; The polycarboxylic acid series third generation high-performance water reducing agent of bringing into use from the nineties in 20th century.The application of water reducer has produced far-reaching influence to concrete technology, and in concrete developing history, it is the leap of concrete technology for the third time after Steel Concrete and prestressed concrete technology that the appearance of high efficiency water reducing agent or superplasticizer is recognized.Water reducer has been considered to indispensable BSA in concrete material.
At present domestic conventional be traditional naphthalene system, melamine series and aliphatic high-efficiency water reducing agent, although it has good dispersion effect to fresh concrete, but the concrete slump of such water reducer preparation through time loss large, in the time being transported to working-yard, must employing scene add water, latter admixing method or strengthen retardant and ensure its mobility, this technique can have a strong impact on the performances such as concrete strength, time of coagulation, shrinkage, weather resistance.And the poisonous formaldehyde material of the many employings of the type high efficiency water reducing agent, be prepared from by polycondensation, inevitably can, to environment, be unfavorable for environment protection, do not meet Sustainable development.
Polycarboxylate high performance water-reducing agent is the high-tech product of concrete admixture industry, and polycarboxylic acid series high efficiency water reducing agent mainly has advantages of following outstanding: low-dosage (0.2-0.5%); High water reducing rate, reinforced effects is remarkable; Concrete mix slump retention excellence, the basic free of losses of the slump in 90min; While comparison, delay time of coagulation less under identical degree of mobilization; Low contraction, low alkalinity, amount of air entrainment are moderate; On molecular structure, degree of freedom is large, and designability is strong, and in admixture manufacturing technology, controllable factor is many, and high performance potentiality are large; Simultaneously owing to not using formaldehyde in building-up process, thereby environment not being polluted, is a kind of Green Product; Use polycarboxylic acids dehydragent to replace cement, thereby to reduce costs with more slag, flyash.Therefore, polycarboxylic acid series high efficiency water reducing agent becomes emphasis and the focus of chemical admixture research and development both at home and abroad at present.
Since having applied for poly carboxylic acid series super plasticizer the first patent from nineteen eighty-two by people such as the Okada of Japanese Kao company, various countries investigator launches further investigation to poly carboxylic acid series super plasticizer.D.C.Darwin etc. deliver in patent USP5393343; introduce the polymkeric substance with hydroxy-acid group of selecting certain molecular weight; by esterification or acylation reaction synthesising graft copolymer, make the dispersiveness of poly carboxylic acid series water reducer and disperse retention to be all largely increased.T.Hirata etc. deliver in patent USP6362364, introduce a kind of special soluble amphoteric type multipolymer water reducer, can be used for general high performance concrete and ultra-high performance concrete, slump reaches 250mm, free of losses in 1.5 hours, is all obtaining promising result aspect diminishing, slump maintenance, strength development.At home, the people such as Lv Shenghua are incorporated into citric acid as side group in poly carboxylic acid macromolecular chain, have synthesized a kind of novel poly carboxylic acid series water reducer.Prepared water reducer under its best proportioning is applied in concrete, and water-reducing rate, up to 32%, has the slow setting time of 5h simultaneously.The people such as Zhang Ming have studied with ethers, ester class, the large monomer of amine and carboxylic-acid monomer synthesizing new poly carboxylic acid series water reducer.At best proportioning: n (ethers APEG): n(ester class MPEG): n(amine NPEG)=0.5:1:0.17, n(MPEG+APEG+NPEG): n (vinylformic acid)=1:3, prepared poly carboxylic acid series water reducer when initiator and chain-transfer agent consumption are respectively 2% and 1.5%, its clean slurry degree of mobilization to cement has a higher conservation rate.In summary, Chinese scholars has had certain research to poly carboxylic acid series super plasticizer, but domestic and international most of patent and document mainly concentrate on the water-reducing rate and the slump maintenance that improve poly carboxylic acid series super plasticizer at present, and introduce for the research that vitriol affects poly carboxylic acid series super plasticizer compatibility problem less, also not for the effectively solution of this problem.
Poly carboxylic acid series super plasticizer receives much concern because of its good performance advantage.But in Practical Project uses, the factor that affects the performance of poly carboxylic acid series super plasticizer performance is a lot, cases of engineering shows, the factor that affects poly carboxylic acid series super plasticizer and component materials of concrete consistency is a lot, as cement specific surface area and size distribution, cement storage time, humidity, cement grinding temperature, sandstone silt content, vitriol etc.Make a general survey of all factors, vitriol is to affect one of poly carboxylic acid series super plasticizer and the most significant factor of component materials of concrete consistency.When applying in concrete works, poly carboxylic acid series super plasticizer cannot avoid the effect with vitriol, this be mainly because: the one, cement, fusion material in concrete all contain vitriol, and vitriol is as the adjustable solidification agent of most cement, its content (taking SO3) limit value is 3.5%, is respectively 3.0% and 4.0% for flyash, ground slag sulphate content (in the SO3) limit value of cement and concrete; The 2nd, sulfonation when traditional water reducer is produced all adopts sulfuric acid, unnecessary sulfuric acid through in alkali and after exist with sulphate form, taking naphthalene water reducer (pulvis masterbatch) as example, its sulphate content can be up to 20%; Other admixtures of concrete often contain vitriol in addition, as swelling agent, hardening accelerator etc.Vitriol affects poly carboxylic acid series super plasticizer compatibility problem has increased the use cost of poly carboxylic acid series super plasticizer in concrete greatly, and the large-scale popularization application of poly carboxylic acid series super plasticizer has been produced to huge negative impact.Therefore, in order to instruct better the engineering application of poly carboxylic acid series super plasticizer, expand the range of application of poly carboxylic acid series super plasticizer, the problem that solution vitriol affects poly carboxylic acid series super plasticizer and component materials of concrete consistency is extremely urgent.
Summary of the invention
For the defect of prior art, the object of this invention is to provide a kind of novel can effectively solution and the organic-silicon-modified poly carboxylic acid series super plasticizer of sulfate resistance type of the compatible problem of concrete component material.
Another object of the present invention is to provide the preparation method of the organic-silicon-modified poly carboxylic acid series super plasticizer of above-mentioned sulfate resistance type.
For reaching above-mentioned purpose, the present invention has adopted following technical scheme:
The organic-silicon-modified poly carboxylic acid series super plasticizer of a kind of sulfate resistance type, its structural formula is as follows:
In formula, j, k, l, m, n represents the mole number of corresponding monomeric unit, j:k:l:m; N=1:3-6:0.5-1:0.5-1:1-3, the integer that j is 4-40; A represents the mole number of repeating unit, the integer that a is 1-99, and R is hydrogen or methyl, M is Na
+.
The preparation method of the organic-silicon-modified poly carboxylic acid series super plasticizer of above-mentioned sulfate resistance type, wherein, comprises the steps:
Step 1: esterification is prepared the large monomer of methoxy polyoxyethylene (methyl) acrylate
(1) get the raw materials ready
Select following monomer a and the ratio of monomer b taking mol ratio as 1:1-5 to get the raw materials ready:
Monomer is general formula (1) expression for a:
CH
3O(CH
2CH
2O)
aH （1）
In formula, the integer that a is 1-99;
Monomer is general formula (2) expression for b:
CH
2＝CH(R)COOH （2）
In formula, R is hydrogen or methyl;
The add-on of stopper is the 0.25-2.5% of carboxylic-acid monomer total amount; Catalyzer is selected from the mixture that the one or both in the vitriol oil, tosic acid is mixed with arbitrary proportion, and add-on is the 1-5% of carboxylic-acid monomer and methoxy poly (ethylene glycol) monomer total amount;
In the reactor that condensation part flow arrangement is housed, add monomer a, be warming up to 80 ± 5 DEG C, after adding stopper to stir, add again monomer b and catalyzer, continue to be warming up to 125 ± 5 DEG C, esterification 5-8 hour, is then cooled to 95-100 DEG C and vacuumizes 2-4h except the water that dereaction generates, and makes the large monomer c of methoxy polyoxyethylene (methyl) acrylate shown in general formula (3):
CH
2＝C(R)COO(CH
2CH
2O)
aCH
3 （3）；
Step 2: synthesizing polycarboxylic acid superplasticizer
(1) get the raw materials ready
Get the raw materials ready in following ratio: the mol ratio of monomer c, monomer d, monomer e, monomer f and monomer g is 1:3-6:0.5-1:0.5-1:1-3;
Monomer is general formula (4) expression for d:
CH
2＝CH(R)COOH （4）
In formula, R is hydrogen or methyl;
Monomer is general formula (5) expression for e:
CH
2＝C(R)SO
3M （5）
In formula, R is hydrogen or methyl, and M is Na
+;
Monomer f is 3-(methacryloxypropyl) propyl trimethoxy silicane, monomer g is vinyl-acetic ester;
(2) configuration solution
Monomer c and monomer d, monomer e, chain-transfer agent and deionized water are made into monomer 1 aqueous solution, and monomer 1 strength of solution is 20wt%-80wt%;
Monomer f, monomer g are mixed and make monomer 2 solution;
The add-on of chain-transfer agent is the 0.5-5wt% of methoxy polyoxyethylene (methyl) acrylate, carboxylic-acid monomer, olefin sulfonic acid class monomer, silicone based monomer and carboxylic acid esters monomer total amount.
It is the ammonium persulfate aqueous solution of 0.2-20% that initiator is selected concentration, add-on is the 1-5wt% of methoxy polyoxyethylene (methyl) acrylate, carboxylic-acid monomer, olefin sulfonic acid class monomer, silicone based monomer and carboxylic acid esters monomer total amount, and initiator solution total concn is 0.2-20wt%.
(3) carry out polyreaction
In reactor, add deionized water, be warming up to 60 ± 5 DEG C, monomer 1,2 solution and initiator solution are added drop-wise to respectively in reactor, wherein monomer 1,2 solution add in 3-3.5h, initiator solution adds in 4-4.5h, after initiator solution drips, at this temperature, continue insulation reaction 2h, after having reacted, be neutralized to pH=7 ± 0.5 with the sodium hydroxide solution of 30% concentration, steam and desolventize and reclaim by underpressure distillation, obtain the organic-silicon-modified poly carboxylic acid series super plasticizer of sulfate resistance type.
The preparation method of the described organic-silicon-modified poly carboxylic acid series super plasticizer of sulfate resistance type, wherein, described chain-transfer agent is 3-thiohydracrylic acid, 3-Thiovanic acid or the mixture of the two.
The preparation method of the described organic-silicon-modified poly carboxylic acid series super plasticizer of sulfate resistance type, wherein, described monomer b and monomer d are vinylformic acid, methacrylic acid or both mixtures; Described monomer e is selected from one or both in sodium allyl sulfonate, methallylsulfonic acid sodium.
The preparation method of the described organic-silicon-modified poly carboxylic acid series super plasticizer of sulfate resistance type, wherein, the stopper in described step 1 is Resorcinol and thiodiphenylamine composite polymerzation inhibitor, wherein Resorcinol and thiodiphenylamine weight ratio are 2-5:1.
The preparation method of the described organic-silicon-modified poly carboxylic acid series super plasticizer of sulfate resistance type, wherein, in the polyreaction of described step 2 (2), in the aqueous solution before titration, add hydrolysis-resisting agent, hydrolysis-resisting agent is selected from a kind of or any two kinds of mixtures that mix with arbitrary proportion in acetone, methyl alcohol, ethanol, ethyl acetate, and add-on is the 50-300wt% of carboxylic acid esters monomer and organosilane monomer total amount.
The present invention also can further realize by the following technical programs:
The preparation method of the described organic-silicon-modified poly carboxylic acid series super plasticizer of sulfate resistance type, wherein, comprises the steps:
Step 1: esterification is prepared the large monomer of methoxy polyoxyethylene (methyl) acrylate
In the reactor that condensation part flow arrangement is housed, add methoxy poly (ethylene glycol), be warming up to 80 ± 5 DEG C, after adding stopper to stir, add again carboxylic-acid monomer and catalyzer, continue to be warming up to 125 ± 5 DEG C, esterification 5-8 hour, is then cooled to 95-100 DEG C and vacuumizes 2-4h except the water that dereaction generates, and makes the large monomer of methoxy polyoxyethylene (methyl) acrylate;
Wherein the mol ratio of methoxy poly (ethylene glycol) and carboxylic-acid monomer is 1:1-5; Stopper adopts Resorcinol and thiodiphenylamine composite polymerzation inhibitor, and add-on is the 0.25-2.5wt% of carboxylic-acid monomer total amount; Catalyzer is selected from a kind of in the vitriol oil, tosic acid or mixture that both mix with arbitrary proportion, and add-on is the 1-5wt% of carboxylic-acid monomer and methoxy poly (ethylene glycol) monomer total amount;
Step 2: synthesizing polycarboxylic acid superplasticizer
(1) get the raw materials ready
Get the raw materials ready in following ratio: the mol ratio of the large monomer of methoxy polyoxyethylene (methyl) acrylate, carboxylic-acid monomer, olefin sulfonic acid class monomer, carboxylic acid esters monomer and silicone based monomer is 1:3-6:0.5-1:0.5-1:1-3;
The methoxy polyoxyethylene making in step 1 (methyl) acrylate and carboxylic-acid monomer, olefin sulfonic acid class monomer, chain-transfer agent and deionized water are made into monomer 1 aqueous solution, and monomer 1 strength of solution is 20wt%-80wt%;
Silicone based monomer, carboxylic acid esters monomer are mixed and make monomer 2 solution;
The add-on of chain-transfer agent is the 0.5-5wt% of methoxy polyoxyethylene (methyl) acrylate, carboxylic-acid monomer, olefin sulfonic acid class monomer, silicone based monomer and carboxylic acid esters monomer total amount.
Initiator add-on is the 1-5wt% of methoxy polyoxyethylene (methyl) acrylate, carboxylic-acid monomer, olefin sulfonic acid class monomer, silicone based monomer and carboxylic acid esters monomer total amount, and initiator solution total concn is 0.2-20%.
(2) carry out polyreaction
In reactor, add deionized water, be warming up to 60 ± 5 DEG C, monomer 1,2 solution and initiator solution are added drop-wise to respectively in reactor, wherein monomer 1,2 solution add in 3-3.5h, initiator solution adds in 4-4.5h, after initiator solution drips, at this temperature, continue insulation reaction 2h, after having reacted, be neutralized to pH=7 ± 0.5 with the sodium hydroxide solution of 30% concentration, steam and desolventize and reclaim by underpressure distillation, obtain the organic-silicon-modified poly carboxylic acid series super plasticizer of sulfate resistance type.
The present invention also can further realize by the following technical programs:
The preparation method of the described organic-silicon-modified poly carboxylic acid series super plasticizer of sulfate resistance type, wherein, described carboxylic-acid monomer is vinylformic acid, methacrylic acid or both mixtures; Described olefin sulfonic acid class monomer is selected from one or both in allylsulfonate, methallylsulfonic acid salt; Described silicone based monomer is 3-(methacryloxypropyl) propyl trimethoxy silicane; Described carboxylic acid esters monomer is vinyl-acetic ester.
The preparation method of the described organic-silicon-modified poly carboxylic acid series super plasticizer of sulfate resistance type, wherein, described chain-transfer agent is 3-thiohydracrylic acid, 3-Thiovanic acid or the mixture of the two.
The preparation method of the described organic-silicon-modified poly carboxylic acid series super plasticizer of sulfate resistance type, wherein, in the polyreaction of described step 2 (2), in the aqueous solution before titration, add hydrolysis-resisting agent, hydrolysis-resisting agent is selected from a kind of or any two kinds of mixtures that mix with arbitrary proportion in acetone, methyl alcohol, ethanol, ethyl acetate, and add-on is the 50-300wt% of carboxylic acid esters monomer and organosilane monomer total amount.
First the present invention prepares the large monomer of methoxy polyoxyethylene (methyl) acrylate taking methyl polyoxyethylene glycol and carboxylic-acid monomer as raw material, and its reaction formula is as follows:
CH
2=CH (R) COOH+CH
3o (CH
2cH
2o)
ah → CH
2=C (R) COO (CH
2cH
2o)
acH
3+ H
2in O formula, a represents the mole number of repeating unit, the integer of a=1-99, and R represents hydrogen or methyl.
Then, with the large monomer of methoxy polyoxyethylene (methyl) acrylate making, with silicone based monomer, carboxylic-acid monomer, carboxylic acid esters monomer and sulphonic acids monomer be that raw material is prepared and obtained product of the present invention by radical polymerization: the organic-silicon-modified poly carboxylic acid series super plasticizer of sulfate resistance type.In whole preparation process, do not use the toxic substances such as formaldehyde, reaction process does not produce waste gas, waste water, waste residue etc., meets the requirement of environmental protection; Synthesis technique is simple to operate, and controllability is strong, is conducive to suitability for industrialized production.
Its reaction formula is:
In formula, j, k, l, m, n represents the mole number of corresponding monomeric unit, j:k:l:m; N=1:3-6:0.5-1:0.5-1:1-3, the integer that j is 4-40; A represents the mole number of repeating unit, the integer that a is 1-99, and R is hydrogen or methyl, M is Na
+.
The organic-silicon-modified poly carboxylic acid series super plasticizer of sulfate resistance type of the present invention is introduced sulfonic group and ester group in poly carboxylic acid series super plasticizer, ensures its high water reducing ability and good slump-loss; According to GB/T8077-2000 " concrete admixture uniformity test method " measure cement paste through time mobility, in the time that the solid volume of the folding of fluidizer is 0.2%, basic free of losses after 120 minutes.Adopt GB8076-1997 to require to carry out the concrete mix slump and water-reducing rate and measure, when the solid volume of folding is 0.2%, water-reducing rate can reach more than 30%, and in fresh concrete 60 minutes, the slump is not lost substantially.The present invention simultaneously has also introduced organosilicon component, silane key can with concrete in silicate form strong chemical bond, thereby the competitive adsorption effect of opposing sulfate ion, when sulfate ion content in concrete is 0 or when 150mmol/L, the adsorptive capacity of the organic-silicon-modified poly carboxylic acid series super plasticizer of sulfate resistance type of the present invention in cement is substantially unchanged.And then effectively solve the concrete compatibility problem of poly carboxylic acid series super plasticizer and high-sulfate content, and greatly reduce the use cost of poly carboxylic acid series super plasticizer in concrete, be conducive to promote applying of poly carboxylic acid series super plasticizer.
Preferably, can be in the preparation process of the large monomer of methoxy polyoxyethylene (methyl) acrylate, adopt Resorcinol and thiodiphenylamine composite polymerzation inhibitor as stopper, compare the single stopper of traditional admixture, can greatly reduce stopper volume, and significantly improve the polymerization inhibition effect of stopper.
Further, can also, in poly carboxylic acid series super plasticizer is synthetic, by add a certain amount of hydrolysis-resisting agent in system, in order to suppress the hydrolysis reaction of silicone based monomer, improve the content of organosilicon component in product.
Brief description of the drawings
Fig. 1, Fig. 2 are that in cement solution, sulfate ion content is 0 o'clock, the adsorptive capacity comparison diagram of different poly carboxylic acid series super plasticizers on cement;
Fig. 3, Fig. 4 are when in cement solution, sulfate ion content is 150mmol/L, the adsorptive capacity comparison diagram of different poly carboxylic acid series super plasticizers on cement.
Embodiment
Below in conjunction with embodiment, further illustrate the present invention:
If no special instructions, described umber is weight part.
Embodiment 1:
Thermometer is being housed, in the four-hole boiling flask of agitator and prolong, add 120g methoxy poly (ethylene glycol) (MPEG, molecular weight 1200), 25.8g methacrylic acid (MAA), 0.45g Resorcinol and 0.12g thiodiphenylamine, being heated to 90 DEG C makes after its whole fusings, add again the 3g vitriol oil to continue to be heated to 125 DEG C of isothermal reaction 5h, being cooled to 98 DEG C vacuumizes after esterification 2h, with NaOH dehydrated alcohol titration acid number, until determination of acid value monohydroxy esterification yield reaches 95% when above, stop heating, can obtain the monomer broad in the middle of poly carboxylic acid series super plasticizer----methoxy polyoxyethylene (methyl) acrylate (MPEG-MAA-1).
Again respectively with the each monomer solution of following proportional arrangement and initiator solution:
Monomer 1 solution: 50g methoxy polyoxyethylene (methyl) acrylate (MPEG-MAA-1), 10g vinylformic acid, 3g methylpropene sodium sulfonate, 1.2g3-thiohydracrylic acid and 27g deionized water;
Monomer 2 solution: 9.5g3-(methacryloxypropyl) propyl trimethoxy silicane, 5g vinyl-acetic ester carboxylic;
Initiator solution: 2.5g ammonium persulphate and 25g deionized water;
In reactor, add 30g deionized water, 25g ethanol, be warming up to 60 ± 5 DEG C, monomer 1,2 solution and initiator solution are added drop-wise to respectively in reactor, and wherein monomer 1,2 solution add in 3h, and initiator solution adds in 4h, after initiator solution drips, at this temperature, continue insulation reaction 2h, after having reacted, be neutralized to pH=7 ± 0.5 with the sodium hydroxide solution of 30% concentration, steam and desolventize and reclaim by underpressure distillation, obtain poly carboxylic acid series super plasticizer SP-1.
Embodiment 2:
Thermometer is being housed, in the four-hole boiling flask of agitator and prolong, add 120g methoxy poly (ethylene glycol) (MPEG, molecular weight 1200), 25.8g methacrylic acid (MAA), 0.45g Resorcinol and 0.12g thiodiphenylamine, being heated to 90 DEG C makes after its whole fusings, add again the 3g vitriol oil to continue to be heated to 125 DEG C of isothermal reaction 5h, being cooled to 98 DEG C vacuumizes after esterification 2h, with NaOH dehydrated alcohol titration acid number, until determination of acid value monohydroxy esterification yield reaches 95% when above, stop heating, can obtain monomer broad in the middle-----methoxy polyoxyethylene (methyl) acrylate (MPEG-MAA-2) of poly carboxylic acid series super plasticizer.
Again respectively with the each monomer solution of following proportional arrangement and initiator solution:
Monomer 1 solution: 50g methoxy polyoxyethylene (methyl) acrylate (MPEG-MAA-2), 10g vinylformic acid, 3g methylpropene sodium sulfonate, 1.6g3-thiohydracrylic acid and 27g deionized water;
Monomer 2 solution: 15g3-(methacryloxypropyl) propyl trimethoxy silicane, 5g vinyl-acetic ester carboxylic;
Initiator solution: 2.7g ammonium persulphate and 25g deionized water;
In reactor, add 30g deionized water, 30g ethanol, be warming up to 60 ± 5 DEG C, monomer 1,2 solution and initiator solution are added drop-wise to respectively in reactor, and wherein monomer 1,2 solution add in 3h, and initiator solution adds in 4h, after initiator solution drips, at this temperature, continue insulation reaction 2h, after having reacted, be neutralized to pH=7 ± 0.5 with the sodium hydroxide solution of 30% concentration, steam and desolventize and reclaim by underpressure distillation, obtain poly carboxylic acid series super plasticizer SP-2.
Embodiment 3:
Thermometer is being housed, in the four-hole boiling flask of agitator and prolong, add 120g methoxy poly (ethylene glycol) (MPEG, molecular weight 2400), 10g vinylformic acid (AA), 12g methacrylic acid (MAA), 1.64g Resorcinol and 0.55g thiodiphenylamine, being heated to 90 DEG C makes after its whole fusings, add again the 4.2g vitriol oil, 1g tosic acid continues to be heated to 125 DEG C of isothermal reaction 5h, being cooled to 98 DEG C vacuumizes after esterification 2h, with NaOH dehydrated alcohol titration acid number, until determination of acid value monohydroxy esterification yield reaches 95% when above, stop heating, can obtain the monomer broad in the middle of poly carboxylic acid series super plasticizer----methoxy polyoxyethylene (methyl) acrylate (MPEG-MAA-3).Again respectively with the each monomer solution of following proportional arrangement and initiator solution:
Monomer 1 solution: 50g methoxy polyoxyethylene (methyl) acrylate (MPEG-MAA-3), 10g vinylformic acid, 3g methylpropene sodium sulfonate, 1.2g3-thiohydracrylic acid and 27g deionized water;
Monomer 2 solution: 9.5g3-(methacryloxypropyl) propyl trimethoxy silicane, 5g vinyl-acetic ester carboxylic;
Initiator solution: 2.5g ammonium persulphate and 25g deionized water;
In reactor, add 30g deionized water, 10g ethanol, 10g acetone, 5g ethyl acetate, be warming up to 56 DEG C, monomer 1,2 solution and initiator solution are added drop-wise to respectively in reactor, wherein monomer 1,2 solution add in 3h, initiator solution adds in 4h, after initiator solution drips, at this temperature, continue insulation reaction 2h, after having reacted, be neutralized to pH=7 ± 0.5 with the sodium hydroxide solution of 30% concentration, steam and desolventize and reclaim by underpressure distillation, obtain poly carboxylic acid series super plasticizer SP-3.
Embodiment 4:
Thermometer is being housed, in the four-hole boiling flask of agitator and prolong, add 120g methoxy poly (ethylene glycol) (MPEG, molecular weight 2400), 22g methacrylic acid (MAA), 1.64g Resorcinol and 0.55g thiodiphenylamine, being heated to 90 DEG C makes after its whole fusings, add again the 4.2g vitriol oil, 1g tosic acid continues to be heated to 125 DEG C of isothermal reaction 5h, being cooled to 98 DEG C vacuumizes after esterification 2h, with NaOH dehydrated alcohol titration acid number, until determination of acid value monohydroxy esterification yield reaches 95% when above, stop heating, can obtain the monomer broad in the middle of poly carboxylic acid series super plasticizer----methoxy polyoxyethylene (methyl) acrylate (MPEG-MAA-4).
Again respectively with the each monomer solution of following proportional arrangement and initiator solution:
Monomer 1 solution: 50g methoxy polyoxyethylene (methyl) acrylate (MPEG-MAA-4), 12g vinylformic acid, 4.4g methylpropene sodium sulfonate, 1.2g3-thiohydracrylic acid and 27g deionized water;
Monomer 2 solution: 12g3-(methacryloxypropyl) propyl trimethoxy silicane, 3.5g vinyl-acetic ester carboxylic;
Initiator is water-soluble: 2.5g ammonium persulphate and 25g deionized water.
In reactor, add 30g deionized water, 10g ethanol, 10g acetone, 5g ethyl acetate, be warming up to 62 DEG C, monomer 1,2 solution and initiator solution are added drop-wise to respectively in reactor, wherein monomer 1,2 solution add in 3h, initiator solution adds in 4h, after initiator solution drips, at this temperature, continue insulation reaction 2h, after having reacted, be neutralized to pH=7 ± 0.5 with the sodium hydroxide solution of 30% concentration, steam and desolventize and reclaim by underpressure distillation, obtain the poly carboxylic acid series super plasticizer SP-4 described in this patent.
Embodiment 5:
Thermometer is being housed, in the four-hole boiling flask of agitator and prolong, add 120g methoxy poly (ethylene glycol) (MPEG, molecular weight 2400), 22g methacrylic acid (MAA), 1.64g Resorcinol and 0.55g thiodiphenylamine, being heated to 90 DEG C makes after its whole fusings, add again the 4.2g vitriol oil, 1g tosic acid continues to be heated to 125 DEG C of isothermal reaction 5h, being cooled to 98 DEG C vacuumizes after esterification 2h, with NaOH dehydrated alcohol titration acid number, until determination of acid value monohydroxy esterification yield reaches 95% when above, stop heating, can obtain the monomer broad in the middle of poly carboxylic acid series super plasticizer----methoxy polyoxyethylene (methyl) acrylate (MPEG-MAA-5).
Again respectively with the each monomer solution of following proportional arrangement and initiator solution:
Monomer 1 solution: 50g methoxy polyoxyethylene (methyl) acrylate (MPEG-MAA-5), 10g vinylformic acid, 4.4g sodium allylsulfonate, 0.86g3-thiohydracrylic acid, 1.5g3-Thiovanic acid and 34g deionized water;
Monomer 2 solution: 12g3-(methacryloxypropyl) propyl trimethoxy silicane, 3.5g vinyl-acetic ester carboxylic;
Initiator solution: 2g ammonium persulphate and 18g deionized water.
In reactor, add 30g deionized water, 10g ethanol, 10g acetone, 5g ethyl acetate, be warming up to 62 DEG C, monomer 1,2 solution and initiator solution are added drop-wise to respectively in reactor, wherein monomer 1,2 solution add in 3h, initiator solution adds in 4h, after initiator solution drips, at this temperature, continue insulation reaction 2h, after having reacted, be neutralized to pH=7 ± 0.5 with the sodium hydroxide solution of 30% concentration, steam and desolventize and reclaim by underpressure distillation, obtain poly carboxylic acid series super plasticizer SP-5.
Embodiment 6:
Thermometer is being housed, in the four-hole boiling flask of agitator and prolong, add 120g methoxy poly (ethylene glycol) (MPEG, molecular weight 1200), 36g methacrylic acid (MAA), 1.8g Resorcinol and 0.4g thiodiphenylamine, being heated to 90 DEG C makes after its whole fusings, add again 4.5g tosic acid to continue to be heated to 125 DEG C of isothermal reaction 5h, being cooled to 98 DEG C vacuumizes after esterification 2h, with NaOH dehydrated alcohol titration acid number, until determination of acid value monohydroxy esterification yield reaches 95% when above, stop heating, can obtain the monomer broad in the middle of poly carboxylic acid series super plasticizer----methoxy polyoxyethylene (methyl) acrylate (MPEG-MAA-6).
Again respectively with the each monomer solution of following proportional arrangement and initiator solution:
Monomer 1 solution: 50g methoxy polyoxyethylene (methyl) acrylate (MPEG-MAA-6), 10g vinylformic acid, 3g methylpropene sodium sulfonate, 1.6g3-thiohydracrylic acid and 27g deionized water;
Monomer 2 solution: 15g3-(methacryloxypropyl) propyl trimethoxy silicane, 5g vinyl-acetic ester carboxylic;
Initiator solution: 2.7g ammonium persulphate and 25g deionized water.
In reactor, add 30g deionized water, 5g ethanol, 10g methyl alcohol, 4g acetone, 8g ethyl acetate, be warming up to 55 DEG C, monomer 1,2 solution and initiator solution are added drop-wise to respectively in reactor, wherein monomer 1,2 solution add in 3h, initiator solution adds in 4h, after initiator solution drips, continues insulation reaction 2h at this temperature, after having reacted, be neutralized to pH=7 ± 0.5 with the sodium hydroxide solution of 30% concentration, steam and desolventize and reclaim by underpressure distillation, obtain poly carboxylic acid series super plasticizer SP-6.
Embodiment 7:
Thermometer is being housed, in the four-hole boiling flask of agitator and prolong, add 120g methoxy poly (ethylene glycol) (MPEG, molecular weight 1200), 36g methacrylic acid (MAA), 1.8g Resorcinol and 0.4g thiodiphenylamine, being heated to 90 DEG C makes after its whole fusings, add again 4.5g tosic acid to continue to be heated to 125 DEG C of isothermal reaction 5h, being cooled to 98 DEG C vacuumizes after esterification 2h, with NaOH dehydrated alcohol titration acid number, until determination of acid value monohydroxy esterification yield reaches 95% when above, stop heating, can obtain the monomer broad in the middle of poly carboxylic acid series super plasticizer----methoxy polyoxyethylene (methyl) acrylate (MPEG-MAA-7).
Again respectively with the each monomer solution of following proportional arrangement and initiator solution:
Monomer 1 solution: 50g methoxy polyoxyethylene (methyl) acrylate (MPEG-MAA-7), 10g vinylformic acid, 3g methylpropene sodium sulfonate, 1.6g3-thiohydracrylic acid and 27g deionized water;
Monomer 2 solution: 15g3-(methacryloxypropyl) propyl trimethoxy silicane, 5g vinyl-acetic ester carboxylic;
Initiator solution: 2.7g ammonium persulphate and 25g deionized water.
In reactor, add 30g deionized water, 5g ethanol, 10g methyl alcohol, 4g acetone, 8g ethyl acetate, be warming up to 55 DEG C, monomer 1,2 solution and initiator solution are added drop-wise to respectively in reactor, wherein monomer 1,2 solution add in 3h, initiator solution adds in 4h, after initiator solution drips, continues insulation reaction 2h at this temperature, after having reacted, be neutralized to pH=7 ± 0.5 with the sodium hydroxide solution of 30% concentration, steam and desolventize and reclaim by underpressure distillation, obtain poly carboxylic acid series super plasticizer SP-7.
Embodiment 8:
Thermometer is being housed, in the four-hole boiling flask of agitator and prolong, add 120g methoxy poly (ethylene glycol) (MPEG, molecular weight 1200), 36g methacrylic acid (MAA), 1.8g Resorcinol and 0.4g thiodiphenylamine, being heated to 90 DEG C makes after its whole fusings, add again 4.5g tosic acid to continue to be heated to 125 DEG C of isothermal reaction 5h, being cooled to 98 DEG C vacuumizes after esterification 2h, with NaOH dehydrated alcohol titration acid number, until determination of acid value monohydroxy esterification yield reaches 95% when above, stop heating, can obtain the monomer broad in the middle of poly carboxylic acid series super plasticizer----methoxy polyoxyethylene (methyl) acrylate (MPEG-MAA-8).
Again respectively with the each monomer solution of following proportional arrangement and initiator solution:
Monomer 1 solution: 50g methoxy polyoxyethylene (methyl) acrylate (MPEG-MAA-8), 8g vinylformic acid, 8g methacrylic acid, 3g sodium allylsulfonate, 1.6g3-thiohydracrylic acid and 27g deionized water;
Monomer 2 solution: 15g3-(methacryloxypropyl) propyl trimethoxy silicane, 5g vinyl-acetic ester carboxylic;
Initiator solution: 4g ammonium persulphate and 25g deionized water.
In reactor, add 30g deionized water, 5g ethanol, 10g methyl alcohol, 4g acetone, 8g ethyl acetate, be warming up to 65 DEG C, monomer 1,2 solution and initiator solution are added drop-wise to respectively in reactor, wherein monomer 1,2 solution add in 3h, initiator solution adds in 4h, after initiator solution drips, continues insulation reaction 2h at this temperature, after having reacted, be neutralized to pH=7 ± 0.5 with the sodium hydroxide solution of 30% concentration, steam and desolventize and reclaim by underpressure distillation, obtain poly carboxylic acid series super plasticizer SP-8.
Comparative example 1:
Thermometer is being housed, in the four-hole boiling flask of agitator and prolong, add 120g methoxy poly (ethylene glycol) (MPEG, molecular weight 1200), 25.8g methacrylic acid (MAA), 3g Resorcinol, being heated to 90 DEG C makes after its whole fusings, add again the 3g vitriol oil to continue to be heated to 125 DEG C of isothermal reaction 5h, being cooled to 98 DEG C vacuumizes after esterification 2h, with NaOH dehydrated alcohol titration acid number, until determination of acid value monohydroxy esterification yield reaches 95% when above, stop heating, can obtain the monomer broad in the middle of poly carboxylic acid series super plasticizer----methoxy polyoxyethylene (methyl) acrylate (MPEG-MAA-1 ').
Again respectively with the each monomer solution of following proportional arrangement and initiator solution:
Monomer 1 solution: 50g methoxy polyoxyethylene (methyl) acrylate (MPEG-MAA-1 '), 10g vinylformic acid, 1g3-thiohydracrylic acid and 27g deionized water;
Initiator solution: 2g ammonium persulphate and 25g deionized water.
In reactor, add 30g deionized water, be warming up to 60 ± 5 DEG C, monomer 1 solution and initiator solution are added drop-wise to respectively in reactor, and wherein monomer 1 solution adds in 3h, and initiator solution adds in 4h, after initiator solution drips, at this temperature, continue insulation reaction 2h, after having reacted, be neutralized to pH=7 ± 0.5 with the sodium hydroxide solution of 30% concentration, steam and desolventize and reclaim by underpressure distillation, obtain the poly carboxylic acid series super plasticizer SP-1 ' of contrast.
Comparative example 2:
Thermometer is being housed, in the four-hole boiling flask of agitator and prolong, add 120g methoxy poly (ethylene glycol) (MPEG, molecular weight 1200), 25.8g methacrylic acid (MAA), 3g Resorcinol, being heated to 90 DEG C makes after its whole fusings, add again the 3g vitriol oil to continue to be heated to 125 DEG C of isothermal reaction 5h, being cooled to 98 DEG C vacuumizes after esterification 2h, with NaOH dehydrated alcohol titration acid number, until determination of acid value monohydroxy esterification yield reaches 95% when above, stop heating, can obtain the monomer broad in the middle of poly carboxylic acid series super plasticizer----methoxy polyoxyethylene (methyl) acrylate (MPEG-MAA-2 ').
Again respectively with the each monomer solution of following proportional arrangement and initiator solution:
Monomer 1 solution: 50g methoxy polyoxyethylene (methyl) acrylate (MPEG-MAA-2 '), 10g vinylformic acid, 3g methylpropene sodium sulfonate, 1g3-thiohydracrylic acid and 27g deionized water;
Initiator solution: 2g ammonium persulphate and 25g deionized water.
In reactor, add 30g deionized water, be warming up to 60 ± 5 DEG C, monomer 1 solution and initiator solution are added drop-wise to respectively in reactor, and wherein monomer 1 solution adds in 3h, and initiator solution adds in 4h, after initiator solution drips, at this temperature, continue insulation reaction 2h, after having reacted, be neutralized to pH=7 ± 0.5 with the sodium hydroxide solution of 30% concentration, steam and desolventize and reclaim by underpressure distillation, obtain poly carboxylic acid series super plasticizer SP-2 '.
Test result
1, the dispersed test of cement slurry
By above-described embodiment 1-8 and comparative example 1 ', 2 ' according to GB/T8077-2000 " Methods for testing uniformity of concrete admixture " measure respectively cement paste through time degree of mobilization.Water cement ratio w/c is 0.29, and the solid volume of polycarboxylate water-reducer folding is that 0.2%(is in cement quality), test temperature is 20 ± 2 DEG C, result is as shown in table 1.
Table 1: the cement slurry dispersiveness of mixing poly carboxylic acid series super plasticizer
2, concrete mix test
Above-described embodiment 1-8 and comparative example 1 ', 2 ' are required to carry out the mensuration of the concrete mix slump and water-reducing rate according to GB8076-1997, the solid volume of polycarboxylate water-reducer folding is 0.2% in cement quality), test temperature is 20 ± 2 DEG C, and result is as shown in table 2.
Table 2: mix the test of poly carboxylic acid series super plasticizer concrete fundamental property
3, the mensuration of cement granules adsorptive capacity
Be 0.5 by above-described embodiment 1-8 and comparative example 1 ', 2 ' according to water-cement ratio, add poly carboxylic acid comb copolymer, stir after 3min, adopt supercentrifuge under the speed of 10000r/min by centrifugal slurry 10min, getting supernatant then filters by pin hole filter, molecule in elimination liquid, finally adopt total organic carbon analyzer (Totalorganiccarbonanalyzer, be called for short TOC,) measure the organic content in centrifugal liquid, after it is converted, the concentration of the superplasticizer after can adsorbing.By concentration poor before and after absorption, and it is converted to known adsorptive capacity.Result as Figure 1-4.
Shown in upper table 1-2 and Fig. 1-4, the organic-silicon-modified poly carboxylic acid series super plasticizer of sulfate resistance type of the present invention according to GB/T8077-2000 " concrete admixture uniformity test method " measure cement paste through time mobility, in the time that the solid volume of folding of fluidizer is 0.2%, basic free of losses after 120 minutes.Adopt GB8076-1997 to require to carry out the concrete mix slump and water-reducing rate and measure, when the solid volume of folding is 0.2%, water-reducing rate can reach more than 30%, and in fresh concrete 60 minutes, the slump is not lost substantially.There is high water reducing ability and good slump-loss.Simultaneously when sulfate ion content in concrete is 0 or when 150mmol/L, the adsorptive capacity of the organic-silicon-modified poly carboxylic acid series super plasticizer of sulfate resistance type of the present invention in cement is substantially unchanged, good with high-sulfate content concrete consistency.Effectively solve high-sulfate content inconsistent problem in poly carboxylic acid series super plasticizer and concrete raw material.
The above, be only preferred embodiment of the present invention, not the present invention done to any pro forma restriction.Any variation being equal to, modification or differentiation etc. that all those skilled in the art utilize technical scheme of the present invention to make above-described embodiment, all still belong in the scope of technical solution of the present invention.
Claims (9)
1. the organic-silicon-modified poly carboxylic acid series super plasticizer of sulfate resistance type, is characterized in that:
Shown in the following formula I of structural formula:
In formula, j, k, l, m, n represents the mole number of corresponding monomeric unit, j:k:l:m; N=1:3-6:0.5-1:0.5-1:1-3, the integer that j is 4-40; A represents the mole number of repeating unit, the integer that a is 1-99, and R is hydrogen or methyl, M is Na
+.
2. the preparation method of the organic-silicon-modified poly carboxylic acid series super plasticizer of sulfate resistance type according to claim 1, is characterized in that:
Comprise the steps:
Step 1: esterification is prepared the large monomer of methoxy polyoxyethylene (methyl) acrylate
(1) get the raw materials ready
Select following monomer a and the ratio of monomer b taking mol ratio as 1:1-5 to get the raw materials ready:
Monomer is general formula (1) expression for a:
CH
3O(CH
2CH
2O)
aH （1）
In formula, the integer that a is 1-99;
Monomer is general formula (2) expression for b:
CH
2=CH(R)COOH （2）
In formula, R is hydrogen or methyl;
The add-on of stopper is the 0.25-2.5% of monomer total amount, and described stopper is Resorcinol and thiodiphenylamine composite polymerzation inhibitor, and wherein Resorcinol and thiodiphenylamine weight ratio are 2-5:1; Catalyzer is selected from one or both mixtures that mix with arbitrary proportion in the vitriol oil, tosic acid, and add-on is the 1-5% of monomer total amount;
(2) esterification
In the reactor that condensation part flow arrangement is housed, add monomer a, be warming up to 80 ± 5 DEG C, after adding stopper to stir, add again monomer b and catalyzer, continue to be warming up to 125 ± 5 DEG C, esterification 5-8 hour, is then cooled to 95-100 DEG C and vacuumizes the water that 2-4h generates except dereaction, make the large monomer c of methoxy polyoxyethylene (methyl) acrylate, monomer is general formula (3) expression for c:
CH
2=C(R)COO(CH
2CH
2O)
aCH
3 （3）；
In formula, R is hydrogen or methyl; A is the integer of 1-99;
Step 2: synthesizing polycarboxylic acid superplasticizer
(1) get the raw materials ready
Get the raw materials ready in following ratio: the mol ratio of monomer c, monomer d, monomer e, monomer f and monomer g is 1:3-6:0.5-1:0.5-1:1-3;
Monomer is general formula (4) expression for d:
CH
2=CH(R)COOH （4）
In formula, R is hydrogen or methyl;
Monomer is general formula (5) expression for e:
CH
2＝C(R)SO
3M （5）
In formula, R is hydrogen or methyl, and M is sodium ion;
Monomer f is 3-(methacryloxypropyl) propyl trimethoxy silicane, monomer g is vinyl-acetic ester;
(2) configuration solution
Monomer c and monomer d, monomer e, chain-transfer agent and deionized water are made into monomer 1 aqueous solution, and monomer 1 strength of solution is 20wt%-80wt%;
Monomer f, monomer g are mixed and make monomer 2 solution;
It is the ammonium persulfate aqueous solution of 0.2-20% that initiator is selected concentration, and add-on is the 1-5wt% of monomer total amount; The add-on of chain-transfer agent is the 0.5-5wt% of monomer total amount
(3) carry out polyreaction
In reactor, add deionized water, be warming up to 60 ± 5 DEG C, monomer 1,2 solution and initiator solution are added drop-wise to respectively in reactor, wherein monomer 1,2 solution add in 3-3.5h, initiator solution adds in 4-4.5h, after initiator solution drips, at this temperature, continue insulation reaction 2h, after having reacted, be neutralized to pH=7 ± 0.5 with the sodium hydroxide solution of 30% concentration, steam and desolventize and reclaim by underpressure distillation, obtain the organic-silicon-modified poly carboxylic acid series super plasticizer of sulfate resistance type.
3. the preparation method of the organic-silicon-modified poly carboxylic acid series super plasticizer of sulfate resistance type according to claim 2, is characterized in that:
Described chain-transfer agent is 3-thiohydracrylic acid, 3-Thiovanic acid or the mixture of the two.
4. the organic-silicon-modified poly carboxylic acid series super plasticizer of sulfate resistance type according to claim 3, is characterized in that:
Described monomer b and monomer d are vinylformic acid, methacrylic acid or both mixtures; Described monomer e is selected from one or both in sodium allyl sulfonate, methallylsulfonic acid sodium.
5. according to the preparation method of arbitrary described organic-silicon-modified poly carboxylic acid series super plasticizer of sulfate resistance type in claim 2-4, it is characterized in that:
In the polyreaction of described step 2 (3), monomer 1,2 solution and initiator solution are added drop-wise to respectively before reactor, in the aqueous solution of reactor, add hydrolysis-resisting agent, hydrolysis-resisting agent is selected from one or both or the mixture that mixes with arbitrary proportion above in acetone, methyl alcohol, ethanol, ethyl acetate, and add-on is the 50-300wt% of monomer f and monomer g total amount.
6. the preparation method of the organic-silicon-modified poly carboxylic acid series super plasticizer of sulfate resistance type according to claim 1, is characterized in that:
Comprise the steps:
Step 1: esterification is prepared the large monomer of methoxy polyoxyethylene (methyl) acrylate
In the reactor that condensation part flow arrangement is housed, add methoxy poly (ethylene glycol), be warming up to 80 ± 5 DEG C, after adding stopper to stir, add again carboxylic-acid monomer and catalyzer, continue to be warming up to 125 ± 5 DEG C, esterification 5-8 hour, is then cooled to 95-100 DEG C and vacuumizes 2-4h except the water that dereaction generates, and makes the large monomer of methoxy polyoxyethylene (methyl) acrylate;
Wherein the mol ratio of methoxy poly (ethylene glycol) and carboxylic-acid monomer is 1:1-5; Stopper adopts Resorcinol and thiodiphenylamine composite polymerzation inhibitor, and wherein Resorcinol and thiodiphenylamine weight ratio are 2-5:1, and add-on is the 0.25-2.5wt% of carboxylic-acid monomer total amount; Catalyzer is selected from one or both mixtures that mix with arbitrary proportion in the vitriol oil, tosic acid, and add-on is the 1-5wt% of carboxylic-acid monomer and methoxy poly (ethylene glycol) monomer total amount;
Step 2: synthesizing polycarboxylic acid superplasticizer
(1) get the raw materials ready
Get the raw materials ready in following ratio: the mol ratio of the large monomer of methoxy polyoxyethylene (methyl) acrylate, carboxylic-acid monomer, olefin sulfonic acid class monomer, carboxylic acid esters monomer and silicone based monomer is 1:3-6:0.5-1:0.5-1:1-3; Described olefin sulfonic acid class monomer is selected from one or both in allylsulfonate, methallylsulfonic acid salt; Described carboxylic acid esters monomer is vinyl-acetic ester; Described silicone based monomer is 3-(methacryloxypropyl) propyl trimethoxy silicane;
The methoxy polyoxyethylene making in step 1 (methyl) acrylate and carboxylic-acid monomer, olefin sulfonic acid class monomer, chain-transfer agent and deionized water are made into monomer 1 aqueous solution, and monomer 1 strength of solution is 20wt%-80wt%;
Silicone based monomer, carboxylic acid esters monomer are mixed and make monomer 2 solution;
The add-on of chain-transfer agent is the 0.5-5wt% of methoxy polyoxyethylene (methyl) acrylate, carboxylic-acid monomer, olefin sulfonic acid class monomer, silicone based monomer and carboxylic acid esters monomer total amount.
Initiator add-on is the 1-5wt% of methoxy polyoxyethylene (methyl) acrylate, carboxylic-acid monomer, olefin sulfonic acid class monomer, silicone based monomer and carboxylic acid esters monomer total amount, and initiator solution total concn is 0.2-20%.
(2) carry out polyreaction
In reactor, add deionized water, be warming up to 60 ± 5 DEG C, monomer 1,2 solution and initiator solution are added drop-wise to respectively in reactor, wherein monomer 1,2 solution add in 3-3.5h, initiator solution adds in 4-4.5h, after initiator solution drips, at this temperature, continue insulation reaction 2h, after having reacted, be neutralized to pH=7 ± 0.5 with the sodium hydroxide solution of 30% concentration, steam and desolventize and reclaim by underpressure distillation, obtain the organic-silicon-modified poly carboxylic acid series super plasticizer of sulfate resistance type.
7. the preparation method of the organic-silicon-modified poly carboxylic acid series super plasticizer of sulfate resistance type according to claim 6, is characterized in that:
Described carboxylic-acid monomer is vinylformic acid, methacrylic acid or both mixtures.
8. the preparation method of the organic-silicon-modified poly carboxylic acid series super plasticizer of sulfate resistance type according to claim 6, is characterized in that:
Described chain-transfer agent is 3-thiohydracrylic acid, 3-Thiovanic acid or the mixture of the two.
9. according to the preparation method of arbitrary described organic-silicon-modified poly carboxylic acid series super plasticizer of sulfate resistance type in claim 6-8, it is characterized in that:
In the polyreaction of described step 2 (2), monomer 1,2 solution and initiator solution are added drop-wise to respectively before reactor, in reactor water solution, add hydrolysis-resisting agent, hydrolysis-resisting agent is selected from one or the mixture in acetone, methyl alcohol, ethanol, ethyl acetate, and add-on is the 50-300wt% of carboxylic acid esters monomer and organosilane monomer total amount.
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| CN104446206B (en) * | 2014-11-28 | 2016-08-17 | 谢静仪 | The concrete of a kind of high water reducing rate, water reducer used and preparation method thereof |
| CN104558434B (en) * | 2014-12-16 | 2017-11-03 | 上海台界化工有限公司 | Siliceous polycarboxylate water-reducer, preparation method and the usage |
| JP6433282B2 (en) * | 2014-12-18 | 2018-12-05 | 株式会社日本触媒 | Cement admixture polymer, cement admixture, and cement composition |
| CN104909599B (en) * | 2015-06-08 | 2017-06-06 | 江苏东浦管桩有限公司 | Polycarboxylate water-reducer, its preparation method and diminishing composition and concrete |
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| CN108034030B (en) * | 2017-12-28 | 2020-07-03 | 科之杰新材料集团有限公司 | Preparation method of polycarboxylic acid with low sensitivity to mud content for concrete |
| CN108102044A (en) * | 2017-12-28 | 2018-06-01 | 科之杰新材料集团有限公司 | A kind of preparation method to the low responsive type polycarboxylate water-reducer of clay content |
| CN108192044B (en) * | 2017-12-28 | 2020-06-26 | 科之杰新材料集团有限公司 | Preparation method of low-mud-content sensitive polycarboxylate superplasticizer for concrete |
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